Polyethersulfone compositions with high heat and good impact resistance

ABSTRACT

Polyethersulfones having Tg greater than about 225° C. and a notched Izod value greater than about 1 ft-lb/in, as measured by ASTM D256, comprise from about 5 mol % to less than about 40 mol % structural units of formula 1; and 
                         
from greater than about 60 mol % to about 95 mol % structural units of formula 2
 
                         
wherein
     R 1 , R 2 , and R 3  are independently at each occurrence a halogen atom, a nitro group, a cyano group, a C 1 -C 12  aliphatic radical, C 3 -C 12  cycloaliphatic radical, or a C 3 -C 12  aromatic radical;   n, m, q are independently at each occurrence integers from 0 to 4; and   Q is a C 3 -C 20  cycloaliphatic radical, or a C 3 -C 20  aromatic radical.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. Nonprovisional patent applicationSer. No. 11/552,276, filed Oct. 24, 2006 now U.S. Pat. No. 8,106,135,which claims the benefit of U.S. application Ser. No. 10/951,299, filedSep. 27, 2004 now abandoned, the entire contents of which areincorporated herein by reference.

BACKGROUND OF THE INVENTION

This invention relates to a polyethersulfone composition, a method tosynthesize the polyethersulfone composition and articles made from thecomposition.

Polyethersulfones are a commercially important family of highperformance, high temperature amorphous thermoplastics. These polymersare of interest to many industries because of their combination of highheat resistance, hydrolysis resistance in steam and hot waterenvironments and good overall chemical resistance. Another reason thesepolymers are of great commercial interest is because in addition tooffering the stated high performance attributes, they are alsotransparent, unlike most semi-crystalline materials which are also usedin high temperature applications.

Polyethersulfones can be produced by a variety of methods. For example,U.S. Pat. Nos. 4,108,837 and 4,175,175 describe the preparation ofpolyarylethers and in particular polyarylethersulfones. U.S. Pat. No.6,228,970 describes the preparation polyarylethersulfones with improvedpolydispersity and lower amounts of oligomers. British patent GB1,264,900 teaches a process for production of a polyethersulfonecomprising structural units derived from 4,4′-biphenol, bisphenol-A(4,4′-isopropylidenediphenol), and 4,4′-dichlorodiphenylsulfone.

The transparency of polyarylethersulfones makes them suitable for use ina variety of applications such as lids and covers for surgical anddental instrument sterilization trays which have to undergo steamautoclave sterilization. In the application just mentioned, the contentsof the sterilization trays may by virtue of the transparency of thepolyethersulfone, be inventoried by visual inspection without exposingthe contents to the environment. Other uses and potential uses ofpolyethersulfones include pet transport containers, and dairy processingequipment, particularly milking machine components. Food and beverageapplications also include uses such as coffee serving carafes andcontainers, microwave cookware, covers for cookware containers, anddoors and windows for appliances, such as rotisserie grills. Theinherent flammability resistance and low smoke release characteristicsof polyethersulfones, particularly those of polyetherphenylsulfone,enhance the utility of such polymers in applications such as masstransit where low heat release on combustion and low toxic smokeemission properties of components used in passenger compartments are ofcritical concern. In the aircraft industry, in particular, the lowflammability and low smoke attributes of polyethersulfones make suchmaterials suitable for use in a variety of aircraft cabin interiorcomponents.

While the currently available polyethersulfones typically possessintermediate heat resistance, it would be desirable to improve theirheat resistance while still maintaining or improving their impactproperties. This would improve the utility of these polymers in a numberof applications, especially in applications such as automotive headlightreflectors, medical trays, aircraft cabin interior components, consumeroriented hot food or beverage service items like tableware and babybottles, pet transport containers, surgical trays, coffee servingcarafes, cookware containers, where improving impact resistance athigher temperatures would be highly desirable. It is axiomatic that thedeficiencies of currently available materials are tolerated becauseviable alternatives are lacking. Key areas for improvement in order tomaximize the utility of polyethersulfones are; physical/mechanicalintegrity at high temperatures, hot water resistance, resistance tocleaning agents, and chemical inertness of the resin under conditions ofuse.

Commercially important polyarylethersulfones include polysulfone (PSU),polyphenylsulfone (PPSU) and polyethersulfone (PES). PSU is a well-knownhigh temperature amorphous engineering thermoplastic resin exhibiting aglass transition temperature (Tg) of about 185° C., high strength,stiffness and toughness over a temperature range of from about −100° to150° C. PSU has an Izod impact strength value (Notched Izod value) ofabout 69 Jm⁻¹ (1.3 ft-lb/in). PSU was commercially introduced in 1965 bythe Union Carbide Corporation and is commercially available as UDEL®polysulfone from Solvay Advanced Polymers LLC. Another versatilepolyarylethersulfone polymer is polyphenylsulfone (PPSU). PPSU iscommercially available from Solvay Advanced Polymers LLC under thetrademark of RADEL®. It has a Tg of 220° C. and an Izod impact strengthvalue of about 700 Jm⁻¹ (13 ft-lb/in).

In various applications it would be highly desirable to producepolyarylethersulfones with higher glass transition temperatures (i.e.increased heat resistance) relative to known polyethersulfones, whilemaintaining or improving the high impact strength typically exhibited bymaterials of the polyethersulfone class. In order to achieve higher heatresistance in polyethersulfones having excellent impact strength,improvements in the design of the polyethersulfone compositions arenecessary.

BRIEF SUMMARY OF THE INVENTION

The present invention provides a polyethersulfone composition comprisingstructural units I

wherein R¹, R², and R³ are independently at each occurrence a halogenatom, a nitro group, a cyano group, a C₁-C₁₂ aliphatic radical, C₃-C₁₂cycloaliphatic radical, or a C₃-C₁₂ aromatic radical; n, m, q areindependently at each occurrence integers from 0 to 4; W is a C₃-C₂₀cycloaliphatic radical or a C₃-C₂₀ aromatic radical; and wherein saidcomposition comprises greater than 5 mole percent aromatic etherstructural units derived from at least one bisphenol having structure II

wherein R³ is independently at each occurrence a halogen atom, a nitrogroup, a cyano group, a C₁-C₁₂ aliphatic radical, C₃-C₁₂ cycloaliphaticradical, or a C₃-C₁₂ aromatic radical; q is independently at eachoccurrence an integer from 0 to 4; W is a C₃-C₂₀ cycloaliphatic radicalor a C₃-C₂₀ aromatic radical.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the effect of co-monomer concentration on productpolyethersulfone glass transition temperature and Notched Izod value forcopolymers of bis(4-chlorophenyl)sulfone, biphenol and fluorenylidenylbisphenol A.

FIG. 2 shows the effect of co-monomer concentration on productpolyethersulfone glass transition temperature and Notched Izod value forcopolymers of bis(4-chlorophenyl)sulfone, biphenol and a bisphenollactam monomer.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of preferred embodiments of the inventionand the examples included therein. In the following specification andthe claims which follow, reference will be made to a number of termswhich shall be defined to have the following meanings.

The singular forms “a”, “an” and “the” include plural referents unlessthe context clearly dictates otherwise.

As used herein, the term “Optional” or “optionally” means that thesubsequently described event or circumstance may or may not occur, andthat the description includes instances where the event occurs andinstances where it does not.

As used herein the term “integer” means a whole number which includeszero. For example, the expression “n is an integer from 0 to 4” means“n” may be any whole number from 0 to 4 including 0.

As used herein, the terms “4,4′-biphenol” and “4,4′-dihydroxybiphenyl”,“4,4′-dihydroxydiphenyl” (CAS No. 92-88-6) are intended to have the samemeaning and may be used interchangeably.

As used herein the term “aliphatic radical” refers to a radical having avalence of at least one comprising a linear or branched array of atomswhich is not cyclic. The array may include hetero atoms such asnitrogen, sulfur, silicon, selenium and oxygen or may be composedexclusively of carbon and hydrogen. Aliphatic radicals may be“substituted” or “unsubstituted”. A substituted aliphatic radical isdefined as an aliphatic radical which comprises at least onesubstituent. A substituted aliphatic radical may comprise as manysubstituents as there are positions available on the aliphatic radicalfor substitution. Substituents which may be present on an aliphaticradical include but are not limited to halogen atoms such as fluorine,chlorine, bromine, and iodine. Substituted aliphatic radicals includetrifluoromethyl, hexafluoroisopropylidene, chloro methyl;difluorovinylidene; trichloromethyl, bromoethyl, bromotrimethylene (e.g.—CH₂CHBrCH₂—), and the like. For convenience, the term “unsubstitutedaliphatic radical” is defined herein to encompass, as part of the“linear or branched array of atoms which is not cyclic” comprising theunsubstituted aliphatic radical, a wide range of functional groups.Examples of unsubstituted aliphatic radicals include allyl,aminocarbonyl (i.e. —CONH₂), carbonyl, dicyanoisopropylidene (i.e.—CH₂C(CN)₂CH₂—), methyl (i.e. —CH₃), methylene (i.e. —CH₂—), ethyl,ethylene, formyl, hexyl, hexamethylene, hydroxymethyl (i.e. —CH₂OH),mercaptomethyl (i.e. —CH₂SH), methylthio (i.e. —SCH₃), methylthiomethyl(i.e. —CH₂SCH₃), methoxy, methoxycarbonyl, nitromethyl (i.e. —CH₂NO₂),thiocarbonyl, trimethylsilyl, t-butyldimethylsilyl,trimethyoxysilypropyl, vinyl, vinylidene, and the like. Aliphaticradicals are defined to comprise at least one carbon atom. A C₁-C₁₀aliphatic radical includes substituted aliphatic radicals andunsubstituted aliphatic radicals containing at least one but no morethan 10 carbon atoms.

As used herein, the term “aromatic radical” refers to an array of atomshaving a valence of at least one comprising at least one aromatic group.The array of atoms having a valence of at least one comprising at leastone aromatic group may include heteroatoms such as nitrogen, sulfur,selenium, silicon and oxygen, or may be composed exclusively of carbonand hydrogen. As used herein, the term “aromatic radical” includes butis not limited to phenyl, pyridyl, furanyl, thienyl, naphthyl,phenylene, and biphenyl radicals. As noted, the aromatic radicalcontains at least one aromatic group. The aromatic group is invariably acyclic structure having 4n+2 “delocalized” electrons where “n” is aninteger equal to 1 or greater, as illustrated by phenyl groups (n=1),thienyl groups (n=1), furanyl groups (n=1), naphthyl groups (n=2),azulenyl groups (n=2), anthraceneyl groups (n=3) and the like. Thearomatic radical may also include nonaromatic components. For example, abenzyl group is an aromatic radical which comprises a phenyl ring (thearomatic group) and a methylene group (the nonaromatic component).Similarly a tetrahydronaphthyl radical is an aromatic radical comprisingan aromatic group (C₆H₃) fused to a nonaromatic component —(CH₂)₄—.Aromatic radicals may be “substituted” or “unsubstituted”. A substitutedaromatic radical is defined as an aromatic radical which comprises atleast one substituent. A substituted aromatic radical may comprise asmany substituents as there are positions available on the aromaticradical for substitution. Substituents which may be present on anaromatic radical include, but are not limited to halogen atoms such asfluorine, chlorine, bromine, and iodine. Substituted aromatic radicalsinclude trifluoromethylphenyl, hexafluoroisopropylidenebis(4-phenyloxy)(i.e. —OPhC(CF₃)₂PhO—), chloromethylphenyl; 3-trifluorovinyl-2-thienyl;3-trichloromethylphenyl (i.e. 3-CCl₃Ph-), bromopropylphenyl (i.e.BrCH₂CH₂CH₂Ph-), and the like. For convenience, the term “unsubstitutedaromatic radical” is defined herein to encompass, as part of the “arrayof atoms having a valence of at least one comprising at least onearomatic group”, a wide range of functional groups. Examples ofunsubstituted aromatic radicals include 4-allyloxyphenoxy, aminophenyl(i.e. H₂NPh-), aminocarbonylphenyl (i.e. NH₂COPh-), 4-benzoylphenyl,dicyanoisopropylidenebis(4-phenyloxy) (i.e. —OPhC(CN)₂PhO—),3-methylphenyl, methylenebis(4-phenyloxy) (i.e. —OPhCH₂PhO—),ethylphenyl, phenylethenyl, 3-formyl-2-thienyl, 2-hexyl-5-furanyl;hexamethylene-1,6-bis(4-phenyloxy) (i.e. —OPh(CH₂)₆PhO—);4-hydroxymethylphenyl (i.e. 4-HOCH₂Ph-), 4-mercaptomethylphemyl (i.e.4-HSCH₂Ph-), 4-methylthiophenyl (i.e. 4-CH₃SPh-), methoxyphenyl,methoxycarbonylphenyloxy (e.g. methyl salicyl), nitromethylphenyl (i.e.-PhCH₂NO₂), trimethylsilylphenyl, t-butyldimethylsilylphenyl,vinylphenyl, vinylidenebis(phenyl), and the like. The term “a C₃-C₁₀aromatic radical” includes substituted aromatic radicals andunsubstituted aromatic radicals containing at least three but no morethan 10 carbon atoms. The aromatic radical 1-imidazolyl (C₃H₂N₂—)represents a C₃ aromatic radical. The benzyl radical (C₇H₈—) representsa C₇ aromatic radical.

As used herein the term “cycloaliphatic radical” refers to a radicalhaving a valence of at least one, and comprising an array of atoms whichis cyclic but which is not aromatic. As defined herein a “cycloaliphaticradical” does not contain an aromatic group. A “cycloaliphatic radical”may comprise one or more noncyclic components. For example, acyclohexylmethy group (C₆H₁₁CH₂—) is a cycloaliphatic radical whichcomprises a cyclohexyl ring (the array of atoms which is cyclic butwhich is not aromatic) and a methylene group (the noncyclic component).The cycloaliphatic radical may include heteroatoms such as nitrogen,sulfur, selenium, silicon and oxygen, or may be composed exclusively ofcarbon and hydrogen. Cycloaliphatic radicals may be “substituted” or“unsubstituted”. A substituted cycloaliphatic radical is defined as acycloaliphatic radical which comprises at least one substituent. Asubstituted cycloaliphatic radical may comprise as many substituents asthere are positions available on the cycloaliphatic radical forsubstitution. Substituents which may be present on a cycloaliphaticradical include but are not limited to halogen atoms such as fluorine,chlorine, bromine, and iodine. Substituted cycloaliphatic radicalsinclude trifluoromethylcyclohexyl,hexafluoroisopropylidenebis(4-cyclohexyloxy) (i.e.—OC₆H₁₁C(CF₃)₂C₆H₁₁O—), chloromethylcyclohexyl;3-trifluorovinyl-2-cyclopropyl; 3-trichloromethykyclohexyl (i.e.3-CCl₃C₆H₁₁—), bromopropylcyclohexyl (i.e. BrCH₂CH₂CH₂C₆H₁₁—), and thelike. For convenience, the term “unsubstituted cycloaliphatic radical”is defined herein to encompass a wide range of functional groups.Examples of unsubstituted cycloaliphatic radicals include4-allyloxycyclohexyl, aminocyclohexyl (i.e. H₂N C₆H₁₁—),aminocarbonylcyclopenyl (i.e. NH₂COC₅H₉—), 4-acetyloxycyclohexyl,dicyanoisopropylidenebis(4-cyclohexyloxy) (i.e. —OC₆H₁₁C(CN)₂C₆H₁₁O—),3-methylcyclohexyl, methylenebis(4-cyclohexyloxy) (i.e.—OC₆H₁₁CH₂C₆H₁₁O—), ethylcyclobutyl, cyclopropylethenyl,3-formyl-2-terahydrofuranyl, 2-hexyl-5-tetrahydrofuranyl;hexamethylene-1,6-bis(4-cyclohexyloxy) (i.e. —OC₆H₁₁(CH₂)₆ C₆H₁₁O—);4-hydroxymethylcyclohexyl (i.e. 4-HOCH₂C₆H₁₁—),4-mercaptomethylcyclohexyl (i.e. 4-HSCH₂C₆H₁₁—), 4-methylthiocyclohexyl(i.e. 4-CH₃SC₆H₁₁—), 4-methoxycyclohexyl, 2-methoxycarbonykyclohexyloxy(2-CH₃OCOC₆H₁₁O—), nitromethylcyclohexyl (i.e. NO₂CH₂C₆H₁₀—),trimethylsilylcyclohexyl, t-butyldimethylsilylcyclopentyl,4-trimethoxysilyethykyclohexyl (e.g. (CH₃O)₃SiCH₂CH₂C₆H₁₀—),vinylcyclohexenyl, vinylidenebis(cyclohexyl), and the like. The term “aC₃-C₁₀ cycloaliphatic radical” includes substituted cycloaliphaticradicals and unsubstituted cycloaliphatic radicals containing at leastthree but no more than 10 carbon atoms. The cycloaliphatic radical2-tetrahydrofuranyl (C₄H₇O—) represents a C₄ cycloaliphatic radical. Thecyclohexylmethyl radical (C₆H₁₁CH₂—) represents a C₇ cycloaliphaticradical.

In one aspect, the present invention relates to polyethersulfones havingTg greater than about 235° C. and a notched Izod value greater thanabout 1 ft-lb/in, and to articles composed thereof. Thepolyethersulfones include from about 5 mol % to less than about 40 mol %structural units of formula 1 and from greater than about 60 mol % toabout 95 mol % structural units of formula 2; particularly from about 10mol % to about 40 mol % structural units of formula 1 and from about 60mol % to about 90 mol % structural units of formula 2; and moreparticularly from about 10 mol % to about 30 mol % structural units offormula 1 and from about 70 mol % to about 90 mol % structural units offormula 2

whereinR¹, R², and R³ are independently at each occurrence a halogen atom, anitro group, a cyano group, a C₁-C₁₂ aliphatic radical, C₃-C₁₂cycloaliphatic radical, or a C₃-C₁₂ aromatic radical;n, m, q are independently at each occurrence integers from 0 to 4; andQ is a C₃-C₂₀ cycloaliphatic radical, or a C₃-C₂₀ aromatic radical.

In particular embodiments, Q may be selected from the group consistingof

More particularly, Q may be

In specific embodiments, Q may be

In other embodiments, the polyethersulfones consist of from about 10 mol% to about 40 mol % structural units of formula 1A and from greater thanabout 60 mol % to about 90 mol % structural units of formula 2,particularly from about 10 mol % to about 30 mol % structural units offormula 1A and from about 70 mol % to about 90 mol % structural units offormula 2; and more particularly from about 15 mol % to about 30 mol %structural units of formula 1A and from about 70 mol % to about 95 mol %structural units of formula 2.

It should be noted that in the context of the present invention, theterm ‘structural units’ refers to internal repeat units, exclusive ofend groups, and when a polyethersulfone is described as ‘consisting of’particular ‘structural units’, other units, especially end units, may bepresent in the polymer.

In particular, the polyethersulfones may consist of from about 10 mol %to about 35 mol % structural units of formula 1A1 and from greater thanabout 65 mol % to about 90 mol % structural units of formula 2B.

In yet other embodiments, the polyethersulfones consist of from about 5mol % to about 25 mol % structural units of formula 1B and from greaterthan about 75 mol % to about 95 mol % structural units of formula 2, andparticularly from about 5 mol % to about 15 mol % structural units offormula 1A and from about 85 mol % to about 95 mol % structural units offormula 2

wherein R², R³, n, m, and q are as defined above and R⁴ is C₁-C₂₀aliphatic radical, a C₃-C₂₀ cycloaliphatic radical, or a C₃-C₂₀ aromaticradical.

In particular, the polyethersulfones may consist of from about 5 mol %to about 25 mol % structural units of formula 1B1 and from greater thanabout 75 mol % to about 95 mol % structural units of formula 2B.

As noted, the present invention provides polyethersulfones comprisingstructural units I

wherein R¹, R², and R³ are independently at each occurrence a halogenatom, a nitro group, a cyano group, a C₁-C₁₂ aliphatic radical, C₃-C₁₂cycloaliphatic radical, or a C₃-C₁₂ aromatic radical; n, m, q areindependently at each occurrence integers from 0 to 4; W is a C₃-C₂₀cycloaliphatic radical or a C₃-C₂₀ aromatic radical; and wherein saidcomposition comprises greater than 5 mole percent aromatic etherstructural units derived from at least one bisphenol having structure II

wherein R³ is independently at each occurrence a halogen atom, a nitrogroup, a cyano group, a C₁-C₁₂ aliphatic radical, C₃-C₁₂ cycloaliphaticradical, or a C₃-C₁₂ aromatic radical; q is independently at eachoccurrence an integer from 0 to 4; W is a C₃-C₂₀ cycloaliphatic radicalor a C₃-C₂₀ aromatic radical. Those skilled in the art will understandthat the term “polyethersulfones comprising structural units I” refersto polyethersulfones comprising the structural units shown in structureI, and that the term is not intended to suggest that thepolyethersulfone comprises “repeat units” having structure I.

Suitable bisphenols having structure II include bisphenols havingstructures III-IX.

Bisphenols III-IX and like bisphenols are available commercially or maybe prepared using methods well known to those skilled in the art.

In one embodiment, the polyethersulfone comprises structural unitsderived from at least bisphenol having structure X

wherein R⁴ is C₁-C₂₀ aliphatic radical, a C₃-C₂₀ cycloaliphatic radical,or an C₃-C₂₀ aromatic radical. Bisphenols having structure X areillustrated by2,3-dihydro-3,3-bis(4-hydroxyphenyl)-2-methyl-1H-isoindol-1-one (CAS No.22749-77-5);2,3-dihydro-3,3-bis(4-hydroxyphenyl)-2cyclohexyl-1H-isoindol-1-one;2,3-dihydro-3,3-bis(4-hydroxyphenyl)-2-phenyl-1H-isoindol-1-one;2,3-dihydro-3,3-bis(4-hydroxyphenyl)-2-(4-fluorophenyl)-1H-isoindol-1-one;and the like.

In one embodiment, the present invention provides polyethersulfones Icomprising at least one structural unit derived from a bisphenolselected from the group consisting of bisphenols III and V.

The polyethersulfones I of the present invention comprise structuralunits derived from at least one biphenol XI

wherein R¹ is defined as in structure I and is independently at eachoccurrence a halogen atom, a nitro group, a cyano group, a C₁-C₁₂aliphatic radical, C₃-C₁₂ cycloaliphatic radical, or a C₃-C₁₂ aromaticradical; and n is independently at each occurrence an integer from 0 to4.

Bisphenols XI are commercially available or may be prepared by methodsknown to those skilled in the art. The biphenol, 4,4′-dihydroxybiphenyl,is a preferred biphenol and is available commercially from ALDRICHChemical Co.

Preferred polyethersulfone compositions provided by the presentinvention typically comprise structural units derived from 4,4′-biphenolin an amount corresponding to from about 5 mole percent to about 95 molepercent of a total amount of aromatic ether structural units present inthe composition, more preferably from about 35 mole percent to about 95mole percent, and even more preferably from about 50 mole percent toabout 95 mole percent.

The polyethersulfone compositions of the present invention exhibit highglass transition temperatures, making them useful materials forapplications requiring resistance to heat. Typically, thepolyethersulfone compositions of the present invention exhibit glasstransition temperatures of greater than about 225° C., more preferablygreater than about 235° C., and even more preferably greater than about250° C.

The polyethersulfone compositions of the present invention exhibitexcellent impact resistance (i.e. Notched Izod test value of greaterthan 1 ft-lb/in). The impact resistance of a polymeric material isconveniently determined using American Standard Test Method D256 (ASTMD256). Typically the polyethersulfone compositions of the presentinvention exhibit Notched Izod test values greater than 1 ft-lb/in,preferably greater than 3 ft-lb/in, and still more preferably greaterthan 8 ft-lb/in as measured using ASTM D256.

As noted, the polyethersulfone compositions of the present inventionexhibit excellent impact resistance (i.e. Notched Izod test value ofgreater than 1 ft-lb/in). Impact resistance is dependent upon molecularweight. In one embodiment the polyethersulfone composition of thepresent invention has a weight average (M_(w)) molecular weight inexcess of 45,000 grams per mole as measured by gel permeationchromatography using polystyrene molecular weight standards inchloroform mobile phase. In another embodiment the polyethersulfonecomposition of the present invention has a weight average (M_(w))molecular weight in excess of 55,000 grams per mole as measured by gelpermeation chromatography using polystyrene molecular weight standards.

In one embodiment the present invention provides a polyethersulfonecomposition comprising structural units XII

wherein W is a C₃-C₂₀ cycloaliphatic radical or a C₃-C₂₀ aromaticradical; and wherein said composition comprises greater than 5 molepercent aromatic ether structural units derived from at least onebisphenol having structure XIII

wherein W is a C₃-C₂₀ cycloaliphatic radical or a C₃-C₂₀ aromaticradical.

Suitable bisphenols XIII include bisphenols having structures III-IX.

In one embodiment, the present invention provides polyethersulfones XIIcomprising at least one structural unit derived from a bisphenolselected from the group consisting of bisphenols III and V.

In one embodiment, the present invention provides polyethersulfones Iwherein said composition comprises greater than 5 mole percent aromaticether structural units derived from at least one bisphenol havingstructure II wherein W is a divalent cycloaliphatic or a divalentaromatic radical selected from the group consisting of structuresXIV-XVIII.

In structures XIV-XVIII the dashed lines indicate the points ofattachment of the divalent radicals to the hydroxyphenylene groups ofthe bisphenol II.

In a particular embodiment of the present invention polyethersulfone Icomprises structural units derived from monomer mixture comprisingfluorenylidene bisphenol-A (FBPA) (Structure III), 4,4′-biphenol and atleast one dihalodiarylsulfone monomer. The monomer mixture comprisingfluorenylidene bisphenol-A monomer III and 4,4′-biphenol monomer isreferred to herein as “a mixture of diphenolic monomers”.

In one particular embodiment, the polyethersulfones of the inventioncomprise structural units derived from a mixture of diphenolic monomerscomprising at least 50 mole percent of 4,4′-biphenol and an amount offluorenylidene bisphenol-A corresponding to less than or equal to 50mole percent, based on the total moles of diphenolic monomers. In otherembodiments the polyethersulfones comprise structural units derived froma mixture of diphenolic monomers comprising at least 70 mole percent of4,4′-biphenol based on total moles of diphenolic monomers. In stillother embodiments the polyethersulfones comprise structural unitsderived from a mixture of diphenolic monomers comprising 50-95 molepercent, preferably 60-95 mole percent or 65-85 mole percent or 70-85mole percent of 4,4′-biphenol based on total moles of diphenolicmonomers.

In one embodiment, the polyethersulfones of the present inventioncomprise, in addition to structural units derived from 4,4′-biphenol andfluorenylidene bisphenol-A monomers, at least one additionaldihydroxybiphenyl monomer. The additional dihydroxybiphenyl monomer maybe any dihydroxybiphenyl other than 4,4′-biphenol including, but are notlimited to, substituted derivatives of 4,4′-biphenol. Suitablesubstituents on one or more of the aromatic rings of the additionaldihydroxybiphenyl monomers comprise iodo, bromo, chloro, fluoro, alkyl,particularly C₁-C₁₀ alkyl, allyl, alkenyl, alkyl ether, cyano and thelike. Additional biphenol monomers may be either symmetrical orunsymmetrical.

In an alternate embodiment, the polyethersulfones of the presentinvention comprise, in addition to structural units derived from4,4′-biphenol and fluorenylidene bisphenol-A monomers, at least oneadditional bisphenol monomer represented by the formula (II).

Aromatic polyethersulfones are known (for example GB Patent 1,078,234,U.S. Pat. No. 4,010,147). They may be prepared, for example, by thereaction of dialkali metal salts of diphenols with dihalodiarylsulfonesin a solvent. The dialkali salts of diphenols may also be produced insitu or may be produced in a separate reaction. The solvent ispreferably an aromatic solvent such as dichlorobenzene (o-DCB),chlorobenzene, xylene, toluene, mesitylene; or a polar aprotic solventsuch as N—C₁-C₅-alkyl caprolactam (for example N-methyl caprolactam,N-ethyl caprolactam, N-n-propyl caprolactam, N-isopropyl caprolactam),N—C₁-C₅-alkyl pyrrolidones (for example N-methylpyrrolidone),N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl sulfoxide,diphenyl sulfone, sulfolane, tetramethyl urea and mixtures thereof. Whenthe solvent employed is a relatively nonpolar solvent such asdichlorobenzene, chlorobenzene, xylene, toluene, or mesitylene, at leastone phase transfer catalysts may be employed in order to achievesynthetically useful reaction rates. Suitable phase transfer catalystsinclude hexaalkylguanidinium chlorides, p-dialkylaminopyridinium salts,bis-guanidinium salts, bis-dialkylaminopyridinium salts,tetraalkylphosphonium salts, and mixtures thereof. When a polar aproticsolvent is employed the use of the phase transfer catalyst may beoptional.

The aromatic polyethersulfones of the present invention are typicallyprepared at temperatures in the range of 130° C. to 320° C., andpreferably at temperatures in the range from 145° C. to 280° C., underpressures of from 0.8 to 10 bar, and still more preferably underpressures of from 1 to 3 bar, most preferably at atmospheric pressure.

The quantity of solvent employed is typically from about 0.5 to about 50parts by weight and preferably from 5 to 35 parts by weight, based onthe total weight of polymer produced.

The polyether sulfones provided by the present invention may berecovered using conventional techniques.

The polyethersulfones according to the invention are thermoplasticscombining high heat resistance with excellent impact resistance andsuperior flame resistance. They may be processed, for example, byextrusion, injection molding, sintering or press molding.

Moldings of any type may be produced. These moldings may be used for anyapplications requiring polyethersulfones of high dimensional stabilityand excellent impact resistance i.e. for example in printing circuitboards, aircraft construction, ovenware for microwave ovens,sterilizable medical instruments, parts of coffee machines, egg boilers,hotwater tanks, pipes and pumps, hair dryers and the like. However, thepolyethersulfones according to the invention are particularly suitablefor films and membranes which are required to show a high heatresistance, high flame resistance and impact resistance.

Standard additives may be added to the polyethersulfones of the presentinvention to the invention, preferably in quantities of from about0.00001 to about 80% by weight and more preferably in quantities of fromabout 0 to about 60% by weight, based on the weight of thepolyethersulfone present in the composition comprising the additive.These additives include such materials as thermal stabilizers,antioxidants, UV stabilizers, plasticizers, visual effect enhancers,extenders, antistatic agents, catalyst quenchers, mold releasing agents,fire retardants, blowing agents, impact modifiers and processing aids.The different additives that can be incorporated into thepolyethersulfones of the present invention are typically commonly usedin resin compounding and are known to those skilled in the art.

Visual effect enhancers, sometimes known as visual effects additives orpigments may be present in an encapsulated form, a non-encapsulatedform, or laminated to a particle comprising polymeric resin. Somenon-limiting examples of visual effects additives are aluminum, gold,silver, copper, nickel, titanium, stainless steel, nickel sulfide,cobalt sulfide, manganese sulfide, metal oxides, white mica, black mica,pearl mica, synthetic mica, mica coated with titanium dioxide,metal-coated glass flakes, and colorants, including but not limited, toPerylene Red. The visual effect additive may have a high or low aspectratio and may comprise greater than 1 facet. Dyes may be employed suchas Solvent Blue 35, Solvent Blue 36, Disperse Violet 26, Solvent Green3, Anaplast Orange LFP, Perylene Red, and Morplas Red 36. Fluorescentdyes may also be employed including, but not limited to, Permanent PinkR (Color Index Pigment Red 181, from Clariant Corporation), Hostasol Red5B (Color Index #73300, CAS #522-75-8, from Clariant Corporation) andMacrolex Fluorescent Yellow 10GN (Color Index Solvent Yellow 160:1, fromBayer Corporation). Pigments such as titanium dioxide, zinc sulfide,carbon black, cobalt chromate, cobalt titanate, cadmium sulfides, ironoxide, sodium aluminum sulfosilicate, sodium sulfosilicate, chromeantimony titanium rutile, nickel antimony titanium rutile, and zincoxide may be employed. Visual effect additives in encapsulated formusually comprise a visual effect material such as a high aspect ratiomaterial like aluminum flakes encapsulated by a polymer. Theencapsulated visual effect additive has the shape of a bead.

Non-limiting examples of antioxidants includetris(2,4-di-tert-butylphenyl)phosphite;3,9-di(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane;3,9-di(2,4-dicumylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane;tris(p-nonylphenyl)phosphite;2,2′,2″-nitrilo[triethyl-tris[3,3′,5,5′-tetra-tertbutyl-1,1′-biphenyl-2′-diyl]phosphite];3,9-distearyloxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane;dilauryl phosphite;3,9-di[2,6-di-tert-butyl-4-methylphenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane;tetrakis(2,4-di-tert-butylphenyl)-4,4′-bis(diphenylene)phosphonite;distearyl pentaerythritol diphosphite; diisodecyl pentaerythritoldiphosphite; 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediolphosphite; tristearyl sorbitol triphosphite;tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite;(2,4,6-tri-tert-butylphenyl)-2-butyl-2-ethyl-1,3-propanediol phosphite;triisodecylphosphite; and mixtures of phosphites containing at least oneof the foregoing. Tris(2,4-di-tert-butylphenyl) phosphite;2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite;bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite are especiallypreferred, as well as mixtures of phosphites containing at least one ofthe foregoing phosphites, and the like.

The polyethersulfones of the present invention may optionally comprisean impact modifier. The impact modifier resin may be added to thepolyethersulfone in an amount corresponding to about 1% to about 30% byweight, based on the total weight of the composition. Suitable impactmodifiers include those comprising one of several different rubberymodifiers such as graft or core shell rubbers or combinations of two ormore of these modifiers. Impact modifiers are illustrated by acrylicrubber, ASA rubber, diene rubber, organosiloxane rubber, ethylenepropylene diene monomer (EPDM) rubber, styrene-butadiene-styrene (SBS)rubber, styrene-ethylene-butadiene-styrene (SEBS) rubber,acrylonitrile-butadiene-styrene (ABS) rubber,methacrylate-butadiene-styrene (MBS) rubber, styrene acrylonitrilecopolymer and glycidyl ester impact modifier.

Non-limiting examples of processing aids include, Doverlube® FL-599(available from Dover Chemical Corporation), Polyoxyter® (available fromPolychem Alloy Inc.), Glycolube P (available from Lonza ChemicalCompany), pentaerythritol tetrastearate, Metablen A-3000 (available fromMitsubishi Rayon), neopentyl glycol dibenzoate, and the like.

Non-limiting examples of UV stabilizers include2-(2′-Hydroxyphenyl)-benzotriazoles, e.g., the 5′-methyl-;3′,5′-di-tert.-butyl-; 5′-tert.-butyl-; 5′-(1,1,3,3-tetramethylbutyl)-;5-chloro-3′,5′-di-tert.-butyl-; 5-chloro-3′-tert.-butyl-5′-methyl-;3′-sec.-butyl-5′-tert.-butyl-; 3′-alpha-methylbenzyl-5′-methyl;3′-alpha-methylbenzyl-5′-methyl-5-chloro-; 4′-hydroxy-; 4′-methoxy-;4′-octoxy-; 3′,5′-di-tert.-amyl-; 3′-methyl-5′-carbomethoxyethyl-;5-chloro-3′,5′-di-tert.-amyl-derivatives; and Tinuvin® 234 (availablefrom Ciba Specialty Chemicals). Also suitable are the2,4-bis-(2′-hydroxyphenyl)-6-alkyl-s-triazines, e.g., the 6-ethyl-;6-heptadecyl- or 6-undecyl-derivatives. 2-Hydroxybenzophenones e.g., the4-hydroxy-; 4-methoxy-; 4-octoxy-; 4-decyloxy-; 4-dodecyloxy-;4-benzyloxy-; 4,2′,4′-trihydroxy-; 2,2′,4,4′-tetrahydroxy- or2′-hydroxy-4,4′-dimethoxy-derivative.1,3-bis-(2′-Hydroxybenzoyl)-benzenes, e.g.,1,3-bis-(2′-hydroxy-4′-hexyloxy-benzoyl)-benzene;1,3-bis-(2′-hydroxy-4′-octyloxy-benzoyl)-benzene or1,3-bis-(2′-hydroxy-4′-dodecyloxybenzoyl)-benzene may also be employed.Esters of optionally substituted benzoic acids, e.g., phenylsalicylate;octylphenylsalicylate; dibenzoylresorcin;bis-(4-tert.-butylbenzoyl)-resorcin; benzoylresorcin;3,5-di-tert.-butyl-4-hydroxybenzoic acid-2,4-di-tert.-butylphenyl esteror -octadecyl ester or -2-methyl-4,6-di-tert.-butyl ester may likewisebe employed. Acrylates, e.g., alpha-cyano-beta, beta-diphenylacrylicacid-ethyl ester or isooctyl ester, alpha-carbomethoxy-cinnamic acidmethyl ester, alpha-cyano-beta-methyl-p-methoxy-cinnamic acid methylester or -butyl ester or N(beta-carbomethoxyvinyl)-2-methyl-indoline maylikewise be employed. Oxalic acid diamides, e.g.,4,4′-di-octyloxy-oxanilide;2,2′-di-octyloxy-5,5′-di-tert.-butyl-oxanilide;2,2′-di-dodecyloxy-5,5-di-tert.-butyl-oxanilide;2-ethoxy-2′-ethyl-oxanilide;N,N′-bis-(3-dimethyl-aminopropyl)-oxalamide;2-ethoxy-5-tert.-butyl-2′-ethyloxanilide and the mixture thereof with2-ethoxy-2′-ethyl-5,4′-di-tert.-butyl-oxanilide; or mixtures of ortho-and para-methoxy- as well as of o- and p-ethoxy-disubstituted oxanilidesare also suitable as UV stabilizers. Preferably the ultraviolet lightabsorber used in the instant compositions is2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;2-[2-hydroxy-3,5-di-(alpha,alpha-dimethylbenzyl)phenyl]-2H-benzotriazole;2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;2-hydroxy-4-octyloxybenzophenone; nickel bis(O-ethyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate);2,4-dihydroxybenzophenone;2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; nickelbutylamine complex with 2,2′-thiobis(4-tert-butylphenol);2-ethoxy-2′-ethyloxanilide; 2-ethoxy-2′-ethyl-5,5′-ditert-butyloxanilideor a mixture thereof.

Non-limiting examples of fire retardants include potassiumnonafluorobutylsulfonate, potassium diphenylsulfone sulfonate, andphosphite esters of polyhydric phenols, such as resorcinol and bisphenolA.

Non-limiting examples of mold release compositions include esters oflong-chain aliphatic acids and alcohols such as pentaerythritol, guerbetalcohols, long-chain ketones, siloxanes, alpha.-olefin polymers,long-chain alkanes and hydrocarbons having 15 to 600 carbon atoms.

The polyethersulfones according to the invention may also be mixed inknown manner with other known polymers to form for example, polymerblends, polymer mixtures, and polymer alloys.

EXAMPLES

The following examples are set forth to provide those of ordinary skillin the art with a detailed description of how the methods claimed hereinare evaluated, and are not intended to limit the scope of what theinventors regard as their invention. Unless indicated otherwise, partsare by weight, temperature is in ° C. Notched Izod values weredetermined to assess impact resistance and were measured according tothe ASTM D256 standard method.

Molecular weights are reported as number average (M_(n)) or weightaverage (M_(w)) molecular weight and were determined by gel permeationchromatography (GPC) analysis, using polystyrene molecular weightstandards to construct a broad standard calibration curve against whichpolymer molecular weights were determined The temperature of the gelpermeation columns was 40° C. and the mobile phase was chloroform with3.75% v/v isopropyl alcohol.

In the following examples, values for glass transition temperature weredetermined by differential scanning calorimetry (DSC) at a heating rateof 20° C. per minute.

Example 1

250 mL-SCALE FBPA/BP COPOLYMERIZATION (30/70 COMPOSITION): Synthesis ofthe disodium salt of fluorenylidene bisphenol A (FBPA): Under an Argonatmosphere 9,9-bis(4-hydroxyphenyl)fluorene (fluorenylidene bisphenol A(FBPA)) (50.6318 g, 0.14449 mol) was dissolved in Argon-degassedmethanol (MeOH) (120 mL). To the slightly yellow solution an aqueous(50.55%) sodium hydroxide solution (22.8659 g, 0.28899 mol) was addeddropwise at room temperature. The color of the solution changed slightlyto orange and precipitation occurred. Addition of 60 mL more of MeOHredissolved the precipitate. The resulting yellow-orange solution wastransferred by means of a peristaltic pump at a constant flow rate of 2mL/min to another reactor, which contained mechanically stirred, hot(170° C.) 1,2-dichlorobenzene (o-DCB) (150 mL). By means of a short-pathdistillation head the MeOH/water mixture was distilled off. When around190 mL were distilled off the temperature was raised to 210° C. Later,50 mL of o-DCB were added and the temperature was raised to 225° C.Distillation was continued until the water content of the distillate wasdetermined to be 20 ppm. Then, the mixture was diluted with dry o-DCB(50 mL) and cooled to room temperature under Argon. The resultingsuspension was filtered under nitrogen. The filter cake was washed withArgon-degassed heptane. The off-white powder was dried at 130° C. undervacuum for 2 days to give 52 g (91%) of the disodium salt of FBPA (FBPANa₂-salt). The salt was used directly for polymerization.

Polymerization: The disodium salt of fluorenylidene bisphenol A(FBPANa₂) (10.2065 g, 25.8799 mmol) and the disodium salt of biphenol(BPNa₂) (13.9275 g, 60.5086 mmol) were weighed into a reaction flaskunder nitrogen atmosphere and suspended in o-dichlorobenzene (o-DCB)(100 mL). Some o-DCB (˜33 g) was distilled out via a short pathdistillation head to dry the mixture, then dichlorodiphenylsulfone(DCDPS) (24.8075 g, 86.3874 mmol) and dry o-DCB (33 g) were added.Again, o-DCB (38 g) was distilled out to dry the mixture. The watercontent of the distillate was determined by Karl Fischer titration to bebetween 10 and 20 ppm. Hexaethylguanidinium chloride (HEGCl) (3.6 ml at0.96 Min o-DCB) was added at 180° C. and the polymerization was started.Aliquots were withdrawn to monitor the molecular weight of the polymer.When the target molecular weight was achieved, the brown honey-coloredsolution was quenched at 180° C. with 10 drops of H₃PO₄ (85%). After 15min, o-DCB (155 mL) was added to dilute the quenched product mixture toabout 10% solids.

Work-up procedure A: The mixture was cooled to 85° C. and while beingstirred at 350 rpm, 1.7 mL of water was added to agglomerate the sodiumchloride. The mixture was then heated to 120° C. to boil off the water.When the bubbling stopped the mixture was filtered hot through denselypacked Celite (˜3-5 mm thick). The resulting clear polymer solution wascooled to room temperature—, precipitated into MeOH using a blender,filtered, and oven dried to afford the product copolymer as an off-whitefluffy powder (30.2 g, 78%). The latter was redissolved in chloroform(190 mL) and precipitated in MeOH.

Work-up Procedure B: In an alternate procedure, the catalyst was removedby direct precipitation into a nonsolvent such as methanol without theaddition of the 1.7 mL of water. After direct precipitation theremaining steps described in Work-up Procedure A were carried out toafford the product polymer.

Work-up Procedure C: In another alternative procedure, the catalyst wasremoved by adsorption using silica gel. The remaining steps described inWork-up Procedure A were carried out to afford the product polymer.

Analysis: Differential scanning calorimetry of the product polymershowed a single glass transition temperature at 240° C.

Example 2

5 L-SCALE FBPA/BP COPOLYMERIZATION (30/70 COMPOSITION): Mixed saltsynthesis: In a magnetically stirred 2000 mL 3-neck round-bottom flaskequipped with a 250 mL addition funnel, FBPA (79.9672 g, 0.22821 mol)was dissolved in Argon-degassed MeOH (400 mL). Under an inert atmospherebiphenol (99.1534 g, 0.53248 mol) was added followed by additional MeOH(350 mL). Aqueous sodium hydroxide (123.5549 g at 49.25 wt %, 1.52138mol) was added dropwise using an addition funnel to the slurry andrinsed-in with MeOH (30 mL). The resulting reddish-orange solution wastransferred by means of a peristaltic pump at ˜6 mL/min intomechanically stirred (200 rpm) hot (165° C.) o-DCB (1480 mL). Theaddition was complete after around 135 minutes and at this point about880 mL of solvents (MeOH/water/o-DCB) had been distilled off. Thedistillation was continued at 185-190° C. until all of the water wasdistilled off. Distillation of o-DCB was continued until about 200 mL ofclear o-DCB were removed. The water content of the last fraction wasdetermined to be 17 ppm. The color of the mixed salt slurry in o-DCB wasalmost white.

Polymerization: To the white slurry of the FBPANa₂ and the BPNa₂ ino-DCB, was added DCDPS (220.62 g, 0.76827 mol) followed by additionalo-DCB (100 mL). The mixture was heated and o-DCB (940 mL) was distilledoff until the solids content was about 29% (29.2%). When about 840 mL ofo-DCB had been distilled off the water content of the distillate wasdetermined to be 9 ppm. The catalyst (32 mL at 0.96 M) was then added tothe reaction mixture at a pot temperature 185° C. A vigorous reflux wasobserved. The polymerization was allowed to proceed. After the finalmolecular weight was reached, the solution was quenched at 180° C. withphosphoric acid (7.1 g of 85% H₃PO₄). After 13 more minutes the mixturewas diluted with o-DCB (1735 mL) to 10% solids. The solution was broughtto 90° C. and water (11 mL) was added while stirring at 350 rpm. Saltcrystals were observed to form in less than a minute. After 15 minutes,the suspension was heated to 135° C. to boil off the water. Then, thehot mixture was drained and filtered through a suitable filtrationdevice. The filtration took less than 15 minutes. The clear solution wascooled to ambient temperature and some precipitation occurred. Themixture was heated to 90° C. and the resultant solution was precipitatedinto MeOH. The fluffy product polymer was dissolved in chloroform (10%solids) and precipitated in MeOH to yield 315 g (92%) of final productpolymer as a fluffy solid. DSC: One T_(g) at 243° C. Notched Izod impacttesting (ASTM D 256) was carried out on ten molded test parts and showedan average value of 3.19 ft-lb/in and a standard deviation of 0.48ft-lb/in.

Example 3

5 L-SCALE FBPA/BP COPOLYMERIZATION (50/50 COMPOSITION): This compositionwas synthesized described in Example 2. The product polymer exhibited asingle glass transition temperature(Tg) at 253.7° C. Notched Izod impacttesting (ASTM D 256) was carried out on ten molded test parts and showedan average value of 1.16 ft-lb/in and a standard deviation of 0.48ft-lb/in.

Example 4

5 L-SCALE FBPA/BP COPOLYMERIZATION (15/85 COMPOSITION): This compositionwas synthesized described in Example 2. The product polymer exhibited asingle glass transition temperature (T_(g)) at 234.8° C. Notched Izodimpact testing (ASTM D 256) was carried out on ten molded test parts andshowed an average value of 8.44 ft-lb/in and a standard deviation of1.63 ft-lb/in.

The data presented in Examples 1-4 illustrate a surprising combinationof very high Tg together with excellent ductility characteristics(Notched Izod above 1 ft-lb/in.) among compositions of the presentinvention. The glass transition temperature and Notched Izod data forthe polyethersulfone compositions of Examples 1-4 are shown graphicallyin FIG. 1. In FIG. 1, 10 shows the correlation between the concentrationof FBPA in the copolymer and the glass transition temperature of thecopolymer. In FIG. 1, 20 shows the correlation between the concentrationof FBPA in the copolymer and the Notched Izod value of the copolymer. Itshould be noted that as the concentration of FBPA-derived structuralunits increases relative to the concentration of biphenol-derivedstructural units, the Notched Izod value observed for the compositiondecreases (FIG. 1). See Example 3 (50% FBPA polysulfone) which exhibitedvery poor performance in Notched Izod testing. A second set of data ispresented in FIG. 2, illustrating properties of copolymers ofbis(4-chlorophenyl)sulfone, biphenol and PPPBP.

FIGS. 1 and 2 show that polyethersulfones according to the presentinvention provide both high Tg and high toughness. For example,polyethersulfones containing 15-30% of units derived from FBPA had Tgranging from about 235° C. to about 245° C. and IZOD from about 8ft-lb/in to about 8 ft-lb/in.; polyethersulfones containing 10-25% ofunits derived from PPPBP had Tg ranging from about 235° C. to about 245°C. and IZOD form about 3 ft-lb/in. to greater than 1 ft-lb/in. Incontrast, a polymer composed of units derived from only biphenol anddichlorodiphenylsulfone, without a bisphenol monomer, had a Tg of 224°C. and a Notched IZOD value of about 13 ft-lb/in. Polymers having nobiphenol monomer had a Tg of about 280° C. and IZOD of less than 1ft-lb/in for the FBPA-containing composition and a Tg of about 270° C.and IZOD of less than 1 ft-lb/in for the PPPBP-containing composition.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood by thoseskilled in the art that variations and modifications can be effectedwithin the spirit and scope of the invention.

What is claimed is:
 1. A polyethersulfone having Tg greater than about235° C. and a notched Izod value greater than about 1 ft-lb/in, saidpolyethersulfone consisting of from about 10 mol % to less than about 40mol % structural units of formula 1A; and

from greater than about 60 mol % to about 90 mol % structural units offormula 2

wherein R² and R³ are independently at each occurrence a halogen atom, anitro group, a cyano group, a C₁-C₁₂ aliphatic radical, C₃-C₁₂cycloaliphatic radical, or a C₃-C₁₂ aromatic radical; and n, m, q areindependently at each occurrence integers from 0 to
 4. 2. Apolyethersulfone according to claim 1, consisting of from about 10 mol %to about 30 mol % structural units of formula 1A; and from about 70 mol% to about 90 mol % structural units of formula
 2. 3. A polyethersulfoneaccording to claim 1, consisting of from about 15 mol % to about 30 mol% structural units of formula 1A; and from about 70 mol % to about 95mol % structural units of formula
 2. 4. A polyethersulfone according toclaim 1, consisting of from about 10 mol % to about less than about 35mol % structural units of formula 1A1; and

from greater than about 65 mol % to about 90 mol % structural units offormula 2B


5. A polyethersulfone according to claim 1, consisting of from about 5mol % to about 15 mol % structural units of formula 1A; and from about85 mol % to about 95 mol % structural units of formula
 2. 6. An articlecomprising a polyethersulfone according to claim 1.